CN109569721A - A kind of preparation method and application of PORPHYRIN IRON modification mesopore silicon oxide composite material - Google Patents
A kind of preparation method and application of PORPHYRIN IRON modification mesopore silicon oxide composite material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and applications of PORPHYRIN IRON modification mesopore silicon oxide composite material.The preparation method includes: to prepare SBA-15；Prepare APTES-SBA-15；PORPHYRIN IRON (FeIX) is taken, after being dispersed in dimethyl sulfoxide (DMSO) solution, APTES-SBA-15 is added, constant temperature persistently stirs centrifugation removal supernatant, it washs and dries, obtain FeIX-SBA-15, i.e. PORPHYRIN IRON modifies mesopore silicon oxide composite material for this.Composite material produced by the present invention can be used for catalytic degradation industrial dye and load anti-tumor drug, can be improved the load factor of drug and realize its slow release, to reduce the Acute Toxicity of doxorubicin hydrochloride while keeping antitumous effect.
Description
Technical field
The present invention relates to a kind of preparation method and applications of PORPHYRIN IRON modification mesopore silicon oxide composite material, belong to catalysis drop
Solve dyestuff, drug delivery system technical field.
Background technique
In recent years, meso pore silicon oxide material is because of its specific surface area with higher, and morphology controllable, cellular structure are regular, hole
The features such as diameter size is continuously adjustable, and surface has the silicone hydroxyl abundant that can be used as active site, is convenient for chemical modification,
Superior performance is shown in absorption, separation and the catalysis reaction of macromolecular.PORPHYRIN IRON can be measured with catalysis oxidation substrate
Hydrogen oxide, glucose and catalytic degradation a variety of environmental contaminants such as hydro carbons, azo dyes etc..But since PORPHYRIN IRON is easily assembled
And inactive dimer is generated, and water-soluble low disadvantage, and cause its catalytic activity to substantially reduce, its is immobilized in high surface
Product material such as macromolecule, silica gel, molecular sieve etc., can be improved its catalytic efficiency.In molecular sieve carrier, the orderly hole of mesoporous material
Road structure is capable of providing special microenvironment, protects the activity of metalloporphyrin.
It is found through retrieval, Patent No. CN2017101643327, the middle promulgated by the State Council that application publication number is CN106925349AU
Bright patent, discloses a kind of solid supported type metal porphyrin catalyst and its application in terms of preparing maleic acid, which is to utilize
Solid supported type metal porphyrin catalyst, furfural are substrate, oxygen as oxidant, and catalysis oxidation furfurol reaction produces maleic acid；Gu
Supported type metal porphyrin catalyst be by metalloporphyrin in conjunction with molecular sieve carrier after obtain.However obtained by the technical solution
Catalyst can not be as the delivery system of carrying medicament.
Summary of the invention
The main object of the present invention is: overcoming the problems, such as of the existing technology, provides a kind of PORPHYRIN IRON and modify mesoporous oxidation
The preparation method of silicon composite, gained composite material can be used not only for degradation industrial dye, moreover it can be used to which carrying medicament carries out
Delivering.In addition, also providing the application of above-mentioned composite material.
Major technique design of the invention is as follows: inventors have found that in the prior art, clearly teaching how could not
Not only PORPHYRIN IRON is immobilized in mesopore silicon oxide, but also form the delivery system of energy carrying medicament.Therefore, inventor is in depth practiced
Finally the technical solution that can effectively overcome disadvantages mentioned above and be different from the prior art has been obtained after research.
The technical solution that the present invention solves its technical problem is as follows:
A kind of preparation method of PORPHYRIN IRON modification mesopore silicon oxide composite material, characterized in that the following steps are included:
S1, SBA-15 is prepared；
S2, APTES-SBA-15 is prepared using SBA-15 made from S1；
S3, PORPHYRIN IRON (FeIX) is taken, after being dispersed in dimethyl sulfoxide (DMSO) solution, be added made from S2
APTES-SBA-15, constant temperature persistently stir, and centrifugation removal supernatant washs and dries, obtains FeIX-SBA-15, this i.e. PORPHYRIN IRON
Modify mesopore silicon oxide composite material.
Further perfect technical solution is as follows for the above method of the present invention:
Preferably, the detailed process of the S1 are as follows:
It takes P123 to be put into three-neck flask, deionized water is added, stirs to clarify；HCl is taken to be added to above-mentioned clear solution
In, constant temperature stirred for the first predetermined time；Under stirring, ethyl orthosilicate is added dropwise, it is predetermined to continue constant temperature stirring second
Time；Above-mentioned reaction solution is transferred in pyroreaction kettle, aging, is washed, supernatant is removed in product centrifugation, and gained powder is ground after dry
End is calcined again removes template, obtains SBA-15；
The detailed process of the S2 are as follows:
SBA-15 made from S1 is taken, toluene is scattered in, 3- aminopropyl triethoxysilane is added dropwise after mixing evenly
(APTES), constant temperature persistently stirs, and after centrifugation removal supernatant, washs, dry, obtains APTES-SBA-15.
It is highly preferred that the w/v of the P123 and deionized water is 8.0g:160ml in S1, stir to clarify
Temperature in the process is room temperature, and the temperature range of the room temperature is 25 DEG C ± 5 DEG C, and the concentration of the HCl is 3.4 ± 0.1M and body
Product is 140 ± 10ml, and the temperature of constant temperature stirring is 40 DEG C ± 5 DEG C, and first predetermined time is 1 ± 0.5 hour, second
Predetermined time is 24 ± 2 hours；The detailed process of the aging are as follows: aging 24 ± 2 hours in 100 DEG C of ± 5 DEG C of baking ovens；It is described to wash
The detailed process washed are as follows: respectively at least three times with water, ethanol washing；The detailed process of the calcining are as follows: forged through 550 DEG C ± 10 DEG C
It burns 6 ± 1 hours；
In S2, the SBA-15, toluene, 3- aminopropyl triethoxysilane w/v be 0.4g:140ml:
1.2ml；The detailed process that the constant temperature persistently stirs are as follows: persistently stirred 8 ± 1 hours in 80 DEG C of ± 5 DEG C of constant temperature oil baths；It is described from
The detailed process of the heart are as follows: 5000 ± 500rpm is centrifuged 5 ± 1 minutes；It is used ethanol washing at least 3 times when washing；The drying
Temperature is 80 DEG C ± 5 DEG C.
Preferably, in S3, detailed process that the constant temperature persistently stirs are as follows: 70 DEG C of ± 5 DEG C of constant temperature oil baths persistently stir 8
± 1 hour；The detailed process of the centrifugation are as follows: 5000 ± 500rpm is centrifuged 5 ± 1 minutes；The detailed process of the washing are as follows: first
With water washing at least 1 time, then with ethanol washing at least 3 times；The detailed process of the drying are as follows: 60 DEG C of ± 5 DEG C of drying are overnight.
The present invention also proposes:
Mesopore silicon oxide composite material is modified using PORPHYRIN IRON made from preparation method described previously.
The present invention also proposes:
A kind of preparation method loading adriamycin composite material, characterized in that the following steps are included:
T1, mesopore silicon oxide composite material and preparation method thereof is modified using previously described PORPHYRIN IRON, prepares PORPHYRIN IRON
Modify mesopore silicon oxide composite material, i.e. FeIX-SBA-15；
T2, doxorubicin hydrochloride (DOX) is taken, is dissolved in deionized water and stirs evenly, DOX solution is made；
T3, FeIX-SBA-15 obtained by T1 is taken, and be dispersed in DOX solution, constant temperature persistently stirs；
T4, T3 acquired solution is centrifuged, removes supernatant, washed, after dry, products therefrom DOX/FeIX-SBA-15, this is
Load adriamycin composite material.
Preferably, in T2, the concentration of the DOX solution is 2 ± 1mg/ml；In T3, what the constant temperature persistently stirred
Detailed process are as follows: continue mixing time 24 ± 2 hours in 37 DEG C of ± 5 DEG C of waters bath with thermostatic control；In T4, the specific mistake of the centrifugation
Journey are as follows: 5000 ± 500rpm is centrifuged 5 ± 1 minutes；The detailed process of the washing are as follows: be washed with water at least 3 times；The drying
Temperature is 60 DEG C ± 5 DEG C.
The present invention also proposes:
Using load adriamycin composite material made from preparation method described previously.
In addition, the present invention also proposes:
The purposes of PORPHYRIN IRON modification mesopore silicon oxide composite material described previously, characterized in that the purposes is for urging
Change degradation industrial dye or catalysis oxidation 3,3',5,5'-tetramethylbenzidine (TMB), alternatively, the purposes is to be used to prepare tool
There is the composite filter membrane of catalytic action, alternatively, the purposes is by load antitumoral compounds to prepare treatment or prevention tumour
The drug or pharmaceutical composition of disease.
The purposes of load adriamycin composite material described previously, characterized in that the purposes is to be used to prepare treatment or pre-
The drug or pharmaceutical composition of preventing tumor disease.
Compared with prior art, beneficial effects of the present invention are as follows:
On the one hand, the present invention is first with 3- aminopropyl triethoxysilane (APTES) to carrying out amination in the duct SBA-15
Modification, then sufficiently reacted with the carboxyl of PORPHYRIN IRON with the amino in the duct SBA-15, modification is completed, in this way, utilizing porphyrin
The analogue enztme activity of iron, gained composite material FeIX-SBA-15 have catalytic activity (such as catalysis oxidation 3,3 ', 5,5 '-tetramethyls
Benzidine (TMB) realizes that composite filter membrane is made for another example come industrial dye acid orange of degrading in the measurement to hydrogen peroxide).
On the other hand, the present invention is using composite material FeIX-SBA-15 as carrier, after loading antitumor drug doxorubicin hydrochloride
Load adriamycin composite material is obtained, the load factor of drug is can be improved and realizes its slow release, thus keeping antitumor
The Acute Toxicity of doxorubicin hydrochloride is reduced while effect.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of SBA-15 and DOX/FeIX-SBA-15 in the embodiment of the present invention 3, and wherein A is
SBA-15, B DOX/FeIX-SBA-15.
Fig. 2 is the solid of DOX/FeIX-SBA-15, SBA-15, FeIX, DOX, FeIX-SBA-15 in the embodiment of the present invention 6
Ultraviolet-visible spectrogram.
Fig. 3 is to be added one into composite material FeIX-SBA-15 and hydrogen peroxide aqueous premix in the embodiment of the present invention 8
Quantitative 3,3 ', the absorption spectrum result figure of solution after 5,5 '-tetramethyl benzidines (TMB) solution reaction different time.
Fig. 4 is that hydrogen peroxide and acid orange system iterate through composite material filter membrane, each film excessively in the embodiment of the present invention 9
Solution absorption spectra result figure afterwards.
Fig. 5 to Fig. 8 is respectively the cell viability histogram of each processing group of the embodiment of the present invention 10, be followed successively by DOX processing group,
FeIX-SBA-15 processing group, DOX-SBA-15 processing group, DOX/FeIX-SBA-15 processing group.
Fig. 9 is that DOX/FeIX-SBA-15 composite material handles different time in PBS buffer solution in the embodiment of the present invention 11
The DOX cumulative release amount result figure measured afterwards.
Specific embodiment
Present invention is further described in detail with reference to the accompanying drawings and in conjunction with the embodiments.But the present invention is not limited to be given
Example out.
Embodiment 1, preparation PORPHYRIN IRON modify mesopore silicon oxide composite material
The preparation method of the PORPHYRIN IRON modification mesopore silicon oxide composite material of the present embodiment, comprising the following steps:
S1, SBA-15 is prepared；
S2, APTES-SBA-15 is prepared using SBA-15 made from S1；
S3, PORPHYRIN IRON (FeIX) is taken, after being dispersed in dimethyl sulfoxide (DMSO) solution, be added made from S2
APTES-SBA-15, constant temperature persistently stir, and centrifugation removal supernatant washs and dries, obtains FeIX-SBA-15, this i.e. PORPHYRIN IRON
Modify mesopore silicon oxide composite material.
In S3, detailed process that the constant temperature persistently stirs are as follows: it is small that 70 DEG C of ± 5 DEG C of constant temperature oil baths persistently stir 8 ± 1
When；The detailed process of the centrifugation are as follows: 5000 ± 500rpm is centrifuged 5 ± 1 minutes；The detailed process of the washing are as follows: first with water
Washing at least 1 time, then with ethanol washing at least 3 times；The detailed process of the drying are as follows: 60 DEG C of ± 5 DEG C of drying are overnight.
Specifically, the detailed process of S1 are as follows:
It takes P123 to be put into three-neck flask, deionized water is added, stirs to clarify；HCl is taken to be added to above-mentioned clear solution
In, constant temperature stirred for the first predetermined time；Under stirring, ethyl orthosilicate is added dropwise, it is predetermined to continue constant temperature stirring second
Time；Above-mentioned reaction solution is transferred in pyroreaction kettle, aging, is washed, supernatant is removed in product centrifugation, and gained powder is ground after dry
End is calcined again removes template, obtains SBA-15；
Wherein, the P123 and the w/v of deionized water are 8.0g:160ml, the temperature during stirring to clarify
Degree is room temperature, and the temperature range of the room temperature is 25 DEG C ± 5 DEG C, the concentration of the HCl be 3.4 ± 0.1M and volume be 140 ±
The temperature of 10ml, the constant temperature stirring are 40 DEG C ± 5 DEG C, and first predetermined time is 1 ± 0.5 hour, the second predetermined time
It is 24 ± 2 hours；The detailed process of the aging are as follows: aging 24 ± 2 hours in 100 DEG C of ± 5 DEG C of baking ovens；The washing it is specific
Process are as follows: respectively at least three times with water, ethanol washing；The detailed process of the calcining are as follows: small through 550 DEG C of ± 10 DEG C of calcinings 6 ± 1
When.
The detailed process of S2 are as follows:
SBA-15 made from S1 is taken, toluene is scattered in, 3- aminopropyl triethoxysilane is added dropwise after mixing evenly
(APTES), constant temperature persistently stirs, and after centrifugation removal supernatant, washs, dry, obtains APTES-SBA-15；
Wherein, the SBA-15, toluene, 3- aminopropyl triethoxysilane w/v be 0.4g:140ml:
1.2ml；The detailed process that the constant temperature persistently stirs are as follows: persistently stirred 8 ± 1 hours in 80 DEG C of ± 5 DEG C of constant temperature oil baths；It is described from
The detailed process of the heart are as follows: 5000 ± 500rpm is centrifuged 5 ± 1 minutes；It is used ethanol washing at least 3 times when washing；The drying
Temperature is 80 DEG C ± 5 DEG C.
Embodiment 2, preparation load adriamycin composite material
The preparation method of the present embodiment load adriamycin composite material, comprising the following steps:
T1, PORPHYRIN IRON modification mesopore silicon oxide composite material, i.e. FeIX-SBA-15 are prepared using embodiment 1；
T2, doxorubicin hydrochloride (DOX) is taken, is dissolved in deionized water and stirs evenly, DOX solution is made；Wherein, described
The concentration of DOX solution is 2 ± 1mg/ml；
T3, FeIX-SBA-15 obtained by T1 is taken, and be dispersed in DOX solution, constant temperature persistently stirs；Wherein, the constant temperature is held
The detailed process of continuous stirring are as follows: continue mixing time 24 ± 2 hours in 37 DEG C of ± 5 DEG C of waters bath with thermostatic control；
T4, T3 acquired solution is centrifuged, removes supernatant, washed, after dry, products therefrom DOX/FeIX-SBA-15, this is
Load adriamycin composite material；Wherein, the detailed process of the centrifugation are as follows: 5000 ± 500rpm is centrifuged 5 ± 1 minutes；It is described to wash
The detailed process washed are as follows: be washed with water at least 3 times；The temperature of the drying is 60 DEG C ± 5 DEG C.
Embodiment 3, scanning electron microscope analysis
The DOX/FeIX-SBA-15 of SBA-15 and embodiment 2 are done into scanning electron microscope analysis, as a result as shown in Figure 1.
It can be seen from the figure that SBA-15 regular appearance, is in corynebacterium, and after modified and load DOX, the regular knot of corynebacterium
Structure is not substantially change, and shows the shape characteristic that will not change SBA-15 in composite material preparation process.
Embodiment 4, constituent content mensure
The FeIX-SBA-15 of embodiment 1 is measured into constituent content through energy-dispersive spectroscopy, the results are shown in Table 1, it is seen that multiple
There are the elements such as C, O, Si, Fe on condensation material surface.
Table 1FeIX-SBA-15 constituent content analysis
Embodiment 5, pore-size distribution test
Prepare comparative example DOX/SBA-15:
(1), doxorubicin hydrochloride (DOX) is taken, is dissolved in deionized water and stirs evenly, DOX solution is made；This step is specific
Parameter is identical as the T2 of embodiment 2；
(2) SBA-15 is taken, and is dispersed in DOX solution, constant temperature persistently stirs；The T3 of this step design parameter and embodiment 2
It is identical；
(3) (2) acquired solution is centrifuged, removes supernatant, washed, after dry, products therefrom DOX/SBA-15；This step is specific
Parameter is identical as the T4 of embodiment 2.
The DOX/FeIX-SBA-15 of SBA-15, DOX/SBA-15, the FeIX-SBA-15 of embodiment 1, embodiment 2 is carried out
The test of BJH pore-size distribution, the results are shown in Table 2.
2 each sample aperture of table
The result shows that the aperture of SBA-15 gradually reduces with the grafting of FeIX and the load of DOX, both show all at
Function is integrated on SBA-15.
The outer visible Spectra Analysis on Edge Recycling of embodiment 6, solid violet
The FeIX-SBA-15 of DOX/FeIX-SBA-15, SBA-15 of embodiment 2, FeIX, DOX, embodiment 1 is consolidated
Body ultraviolet-visible spectrum analysis.
As a result as shown in Figure 2.In figure, the characteristic absorption peak of the visible FeIX of the spectrogram of FeIX-SBA-15 shows FeIX's
Success is grafted；The characteristic absorption peak of visible FeIX and DOX in the spectrogram of DOX/FeIX-SBA-15 shows that FeIX is successfully transferred
It is connected on SBA-15 and DOX is successfully loaded on FeIX-SBA-15.
Embodiment 7, load capacity analysis
The DOX/SBA-15 of a certain amount of embodiment 5 and the DOX/FeIX-SBA-15 of embodiment 2 are weighed, uses hydrogen fluorine respectively
Evaporation of solvent after acid dissolution is added deionized water constant volume to 2ml, measures 480nm wave using ultraviolet-visible spectrophotometry
The absorbance value of strong point calculates the content of doxorubicin hydrochloride according to standard curve, and the drug that DOX is calculated according to formula is negative
Carrying capacity (DLC):
DLC (wt.%)=(medication amount/sample gross mass loaded in sample) × 100%.
The carrying drug ratio that the carrying drug ratio that DOX/SBA-15 is calculated is 1.14%, DOX/FeIX-SBA-15 is 4.27%, should
The result shows that the grafting of PORPHYRIN IRON improves the drug carrying capacity of SBA-15.
Embodiment 8, FeIX-SBA-15 catalysis oxidation TMB
A certain amount of 3,3 ', 5,5 '-four are added into the FeIX-SBA-15 and hydrogen peroxide aqueous premix of embodiment 1
Methyl biphenyl amine (TMB) solution measures the absorption spectrum of solution after reaction different time using ultraviolet-visible spectrophotometry.Knot
Fruit sees Fig. 3, is the characteristic peak of known TMB oxidation product at 651nm, it can be seen from the figure that the reaction time is longer, peak intensity
It is bigger, show that TMB is bigger by the degree of catalysis oxidation.
Embodiment 9, FeIX-SBA-15 degradation acid orange
The FeIX-SBA-15 of embodiment 1 is fixed to acquisition composite material filter membrane on filter membrane, by hydrogen peroxide and acid orange
System iterates through the composite material filter membrane, and records each solution absorption spectra crossed after film within the scope of 550-750nm.Experiment
As a result see Fig. 4, be somebody's turn to do the result shows that FeIX-SBA-15 can effectively degrade acid orange, and react over time and more completely；
Also, the composite material filter membrane can be realized the sustaining degradation to acid orange.
Embodiment 10, antitumor cytolytic activity
The DOX of various concentration, the FeIX-SBA-15 of embodiment 1, embodiment 5 are measured using CCK-8 kit respectively
DOX/SBA-15, embodiment 2 DOX/FeIX-SBA-15 act on the survival rate of cell after A549 cell 24 hours, be used in combination
The IC50 value of SPSS software calculating each sample.
As a result as shown in Fig. 5 to Fig. 8, as knowen from these results, with the increase of activity, cell viability is reduced, is deposited
In dose-dependent effect.
Free DOX has apparent anti-tumor activity, and IC50 value is 0.50 μ g/ml；FeIX-SBA-15 has certain
Anti-tumor activity, IC50 value are 35.36 μ g/ml；DOX/FeIX-SBA-15 also has anti-tumor activity, and IC50 value is
12.55μg/ml；The IC50 value of DOX/SBA-15 is 58.80 μ g/ml.
About DOX/FeIX-SBA-15, DOX/SBA-15, being converted according to 7 gained load factor of embodiment is DOX, then DOX/
It is about 0.67 μ g/ml that the IC50 value of DOX, which is about the IC50 value of DOX in 0.54 μ g/ml, DOX/SBA-15, in FeIX-SBA-15.
It can be seen that DOX/FeIX-SBA-15 does not influence the anti-tumor activity of DOX substantially.
Embodiment 11, in-vitro simulated release measurement
A certain amount of DOX/FeIX-SBA-15 composite material is placed in the PBS buffer solution of pH 7.0, under 37 DEG C of water-baths with
200 turns of mixing speed per minute persistently stirs, and point takes out 2ml solution in different times, while the PBS for supplementing same volume is slow
Fliud flushing, the reaction solution of taking-up measure the absorbance value at 480nm after filtering, using ultraviolet-visible spectrophotometry, and with this
Calculate the cumulative release amount of DOX.Experimental result is shown in Fig. 9.
By Fig. 9 result it is found that with the time growth, DOX constantly releases from DOX/FeIX-SBA-15, and
Early period, release efficiency was high, and later period rate of release is gradually reduced.This shows that DOX/FeIX-SBA-15 is able to achieve slowly releasing for DOX
It puts.
In addition to the implementation, the present invention can also have other embodiments.It is all to use equivalent substitution or equivalent transformation shape
At technical solution, fall within the scope of protection required by the present invention.
Claims (10)
1. a kind of preparation method of PORPHYRIN IRON modification mesopore silicon oxide composite material, characterized in that the following steps are included:
S1, SBA-15 is prepared；
S2, APTES-SBA-15 is prepared using SBA-15 made from S1；
S3, PORPHYRIN IRON is taken, after being dispersed in dimethyl sulfoxide solution, APTES-SBA-15 made from S2 is added, constant temperature is held
Continuous stirring, centrifugation removal supernatant, washs and dries, obtain FeIX-SBA-15, and i.e. PORPHYRIN IRON modifies mesopore silicon oxide composite wood for this
Material.
2. preparation method according to claim 1, characterized in that the detailed process of the S1 are as follows:
It takes P123 to be put into three-neck flask, deionized water is added, stirs to clarify；HCl is taken to be added in above-mentioned clear solution, it is permanent
Temperature the first predetermined time of stirring；Under stirring, ethyl orthosilicate is added dropwise, continues constant temperature and stirred for the second predetermined time；
Above-mentioned reaction solution is transferred in pyroreaction kettle, aging, is washed, supernatant is removed in product centrifugation, and gained powder is ground after dry again
Template is removed in calcining, obtains SBA-15；
The detailed process of the S2 are as follows:
SBA-15 made from S1 is taken, toluene is scattered in, 3- aminopropyl triethoxysilane is added dropwise after mixing evenly, constant temperature is held
Continuous stirring after centrifugation removes supernatant, is washed, dry, obtains APTES-SBA-15.
3. preparation method according to claim 2, characterized in that
In S1, the w/v of the P123 and deionized water is 8.0g:160ml, the temperature during stirring to clarify
For room temperature, the temperature range of the room temperature is 25 DEG C ± 5 DEG C, the concentration of the HCl be 3.4 ± 0.1M and volume be 140 ±
The temperature of 10ml, the constant temperature stirring are 40 DEG C ± 5 DEG C, and first predetermined time is 1 ± 0.5 hour, the second predetermined time
It is 24 ± 2 hours；The detailed process of the aging are as follows: aging 24 ± 2 hours in 100 DEG C of ± 5 DEG C of baking ovens；The washing it is specific
Process are as follows: respectively at least three times with water, ethanol washing；The detailed process of the calcining are as follows: small through 550 DEG C of ± 10 DEG C of calcinings 6 ± 1
When；
In S2, the SBA-15, toluene, 3- aminopropyl triethoxysilane w/v be 0.4g:140ml:
1.2ml；The detailed process that the constant temperature persistently stirs are as follows: persistently stirred 8 ± 1 hours in 80 DEG C of ± 5 DEG C of constant temperature oil baths；It is described from
The detailed process of the heart are as follows: 5000 ± 500rpm is centrifuged 5 ± 1 minutes；It is used ethanol washing at least 3 times when washing；The drying
Temperature is 80 DEG C ± 5 DEG C.
4. preparation method according to claim 1, characterized in that in S3, detailed process that the constant temperature persistently stirs
Are as follows: 70 DEG C of ± 5 DEG C of constant temperature oil baths persistently stir 8 ± 1 hours；The detailed process of the centrifugation are as follows: 5000 ± 500rpm centrifugation 5 ±
1 minute；The detailed process of the washing are as follows: first with water washing at least 1 time, then with ethanol washing at least 3 times；The tool of the drying
Body process are as follows: 60 DEG C of ± 5 DEG C of drying are overnight.
5. modifying mesopore silicon oxide composite material using PORPHYRIN IRON made from any one of the Claims 1-4 preparation method.
6. a kind of preparation method for loading adriamycin composite material, characterized in that the following steps are included:
T1, mesopore silicon oxide composite material and preparation method thereof, preparation are modified using the described in any item PORPHYRIN IRONs of Claims 1-4
It obtains PORPHYRIN IRON and modifies mesopore silicon oxide composite material, i.e. FeIX-SBA-15；
T2, doxorubicin hydrochloride is taken, be dissolved in deionized water and stirred evenly, DOX solution is made；
T3, FeIX-SBA-15 obtained by T1 is taken, and be dispersed in DOX solution, constant temperature persistently stirs；
T4, T3 acquired solution is centrifuged, removes supernatant, washed, after dry, products therefrom DOX/FeIX-SBA-15, this is loaded
Adriamycin composite material.
7. preparation method according to claim 6, characterized in that in T2, the concentration of the DOX solution is 2 ± 1mg/
ml；In T3, detailed process that the constant temperature persistently stirs are as follows: continue mixing time 24 ± 2 in 37 DEG C of ± 5 DEG C of waters bath with thermostatic control
Hour；In T4, the detailed process of the centrifugation are as follows: 5000 ± 500rpm is centrifuged 5 ± 1 minutes；The detailed process of the washing
Are as follows: it is washed with water at least 3 times；The temperature of the drying is 60 DEG C ± 5 DEG C.
8. loading adriamycin composite material using the preparation method of claim 6 or 7 is obtained.
9. PORPHYRIN IRON described in claim 5 modification mesopore silicon oxide composite material purposes, characterized in that the purposes be for
Catalytic degradation industrial dye or catalysis oxidation 3,3',5,5'-tetramethylbenzidine, alternatively, the purposes is to be used to prepare to have
The composite filter membrane of catalytic action, alternatively, the purposes is to treat or prevent tumour disease by load antitumoral compounds to prepare
The drug or pharmaceutical composition of disease.
10. loading the purposes of adriamycin composite material described in claim 8, characterized in that the purposes is to be used to prepare treatment
Or the drug or pharmaceutical composition of prevention tumor disease.
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